CN103506165A - Preparation method of large-aperture fat hydrogenation catalyst - Google Patents
Preparation method of large-aperture fat hydrogenation catalyst Download PDFInfo
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- CN103506165A CN103506165A CN201310472730.7A CN201310472730A CN103506165A CN 103506165 A CN103506165 A CN 103506165A CN 201310472730 A CN201310472730 A CN 201310472730A CN 103506165 A CN103506165 A CN 103506165A
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Abstract
The invention relates to a preparation method of a large-aperture fat hydrogenation catalyst. The preparation method is characterized in that nickel is used as an active constituent, alkaline-earth metal is used as an additive, titanium aluminium oxide is used as a compound carrier, and amine oxide used as a pore-enlarging additive is added during the preparation process. The specific surface area of the catalyst is 200 to 400 m<2>/g, the pore volume is 0.5 to 2.0 m<3>/g, and the average pore diameter is 9 to 20 nm; the catalyst comprises 5 to 30 wt% of nickel serving as an effective active constituent, 0.01 to 5 wt% of the additive, 10 to 50 wt% of stearic acid, and the balance of the titanium aluminium oxide serving as the carrier; by the overall weight of the carrier, the content of titanium oxide is 0 to 50 wt%. The catalyst prepared through the method has the advantage that under the process conditions that the use amount of the catalyst is 0.1%, the reaction pressure is 2.0 MPa, the reaction temperature is 200 DEG C and the reaction time is 90 min, the iodine value of palm oil can be reduced from 56.0 to lower than 1.0.
Description
Technical field
The present invention relates to oil hydrogenation catalyst technical field, specifically the preparation method of a kind of large aperture oil hydrogenation catalyst.Say more specifically and in preparation process, add amine oxide as expanding agent, adopt the precipitation method to prepare the method for Ni base oil fat hydrogenation catalyst, and the application technology of this catalyst in consaturated oil hydrogenation.
Background technology
HYDROGENATION OF OILS AND FATS is by undersaturated vegetable and animals oils, and by catalyst, by its pair of key process of hydrogenation partially or completely, its main purpose is: reduce grease degree of unsaturation, improve fusing point, increase solid fats content; Improve grease to oxygen and hot stability; Improve color and luster, fragrance and the local flavor of grease.
The research of oil hydrogenation catalyst is the focus that oil hydrogenation industry is paid close attention to, and commercial Application be take nickel-base catalyst as main at present, is characterized in active high, and reaction temperature is low, but selectively slightly poor, easily poisoning; The catalyst based activity of Cu is less, but selectively good; The catalyst based activity of Pd, Ru is the highest, but financial cost has limited its commercial Application.
Aspect prepared by oil hydrogenation catalyst, patent US4510029 and US4519951 have announced with α-Al respectively
2o
3and γ-Al
2o
3ni-Al for carrier
2o
3catalyst.These patents are selecting to have done some work that are highly profitable aspect novel carriers.Chinese patent CN101347734A has announced the large hole nickel-based catalyst preparation method that a kind of aluminium oxide is carrier, can make the larger nickel-base catalyst in aperture, but its specific area is less, and nickel content is higher, and preparation cost is higher.CN102513114 has announced a kind of preparation of antitoxin type catalyst, has added Rare Earth Lanthanum, cerium in catalyst.CN85103783 has announced a kind of high activity Ni-Pd catalyst, but too high this catalyst that makes of its preparation cost loses competitiveness.
Advantage of the present invention is to have the oil hydrogenation catalyst simultaneously compared with bigger serface with larger aperture by adding amine oxide as expanding agent in preparation process, making, thereby improves active component utilization rate, improves catalyst activity, reduces production costs.
Summary of the invention
The object of the invention is to by selecting amine oxide as expanding agent, when making the catalyst of preparation keep compared with bigger serface, there is larger aperture, improve the mass transfer conditions of reactant and product in oil hydrogenation course of reaction, thereby improve the utilization rate of catalyst activity component, improve catalyst activity and selectivity.
The present invention is the preparation method of a kind of large aperture oil hydrogenation catalyst, it is characterized in that:
The concrete operation step of Kaolinite Preparation of Catalyst is as follows:
1) first certain density aluminum sulfate solution and sodium aluminate solution stream are joined in neutralization reaction still, it is 50-95 ℃ that whole reaction system keeps reaction temperature under mechanical agitation, within approximately 1 hour, neutralization reaction finishes, aging reaction liquid, control ageing time after 30-60 minute, appropriate titanium tetrachloride aqueous solution is squeezed in boehmite slurries, slowly added the ammoniacal liquor regulator solution pH to 6.5-7.5 of suitable concentration; Reaction finishes to continue aging 30-60 minute;
2) aging end, keep temperature 60-90 ℃, nickel salts solution, the alkaline sedimentation agent solution, the compounding agent solution that have added amine oxide expanding agent are joined in neutralization reaction still, feed time was controlled in 1-2 hour, after neutralization reaction, keep synthermal aging 0.5-3.0 hour; Aging reaction solution finishes rear filtration slip, with deionized water, ethanol washing leaching cake post-drying, pulverizing, roasting, and at 300-500 ℃, logical N
2, H
2gaseous mixture: N
2/ H
2=3:1 volume ratio; Reduce 3-5 hour, add in stearic acid, stir, cooling curing granulating and forming gets final product to obtain oil hydrogenation catalyst;
By above-mentioned preparation method, specific surface area of catalyst is 200-400m
2/ g, pore volume is 0.5-2.0m
3/ g, average pore size is 9-20nm; Catalyst consists of: effective active component nickel 5-30wt%, and auxiliary agent 0.01-5wt%, stearic acid 10-50wt%, all the other are titanium aluminum oxide carrier; With the total restatement of carrier, titanium oxide content is 0-50wt%;
Described aluminum sulfate solution concentration is 0.10-2.00mol/L, and described sodium aluminate solution concentration is 2.00-6.00mol/L;
The amine oxide expanding agent of described interpolation refers to one or both in the amino dimethyl oxidation of alkyl dimethyl amine oxide, alkyl diethyl alcohol radical Yang Huan and alkane acyl third amine, does not comprise other materials;
The amine oxide expanding agent addition of described interpolation accounts for the 0.05-5% of catalyst quality;
Described soluble nickel salting liquid is selected from as one or more in nickel chloride, nickelous sulfate, nickel nitrate or nickel acetate; Concentration is 5-30wt%;
Described alkaline sedimentation agent solution is selected from one or more in sodium carbonate, sodium acid carbonate, sodium acetate, NaOH or ammonium bicarbonate soln; Concentration is 5-20wt%;
Described compounding agent solution is one or more in nitrate, carbonate, acetate or the chloride solution of alkali earth metal; Concentration is 2-60wt%.
Catalyst prepared by the present invention is at catalyst amount 0.1%, reaction pressure 2.0MPa, and 200 ℃ of reaction temperatures, under reaction time 90min process conditions, can make palm oil iodine number be down to below 1.0 by 56.0.
The specific embodiment
Embodiment 1
The sodium aluminate solution that the aluminum sulfate solution that is 0.90mol/L by 450mL concentration and 420mL concentration are 6.00mol/L stream add in neutralization reaction still, and it is 85 ℃ that reaction temperature is controlled, speed of agitator 300rpm.Within approximately 1 hour, neutralization reaction finishes, aging reaction slurries 45 minutes.After aging end, controlling temperature is 70 ℃, and the aqueous solution containing 230.0g titanium tetrachloride is squeezed in aluminium oxide slurries, slowly adds 15% ammoniacal liquor regulator solution pH to 7.0, reacts complete, continues aging slurries 45 minutes.
Aging end, starts and stirs and heating system to 80 ℃, the nickel nitrate solution that is 0.10mol/L by 1600mL concentration; Added the Na of 3.0g octadecyl dimethyl amine oxide
2cO
3solution 500mL, its concentration is 0.4mol/L; 200mL concentration is that the calcium chloride solution of 0.06mol/L at the uniform velocity adds in reactor, and feed time was controlled in 1.0 hours, and material liquid keeps synthermal aging slurries 3.0 hours after all adding.Then filter slip, with deionized water and ethanol washing leaching cake, dry after 3.0 hours for 110 ℃ and pulverize, 500 ℃ of roasting 3.0h.500 ℃ of logical N
2, H
2gaseous mixture (N
2/ H
2=3:1 volume ratio) reduce 4.0 hours, cooling.Then under nitrogen protection, the catalyst powder of reduction is added in stearic acid, catalyst precursor and stearic acid weight ratio are 1:3.Stir, cooling curing granulating and forming makes oil hydrogenation catalyst.Catalyst nitrogen determining adsorption the results are shown in Table 1.
The catalyst of preparation adopts palm oil hydrogenation reaction to evaluate, and adds 2500g palm oil in 5L autoclave, 2.5g catalyst, and Hydrogen Vapor Pressure 2.0MPa, 200 ℃ of reaction temperatures, stir under 600rpm and react 90min.Product iodine number is analyzed, and the lower explanation catalyst activity of iodine number is higher.Palm oil hydrogenation reaction evaluation result is in Table 1.
Comparative example 1. takes 2.5g import catalyst 1# and carries out palm oil hydrogenation evaluation response, and appreciation condition is with embodiment 1.Palm oil hydrogenation reaction evaluation result is in Table 1.
Comparative example 2. takes 2.5g import catalyst 2# and carries out the evaluation of palm oil hydrogenation reaction, and appreciation condition is with embodiment 1.Palm oil hydrogenation reaction evaluation result is in Table 1.
Embodiment 2
Change the addition of octadecyl dimethyl amine oxide in embodiment 1 into 6.0g, other are with embodiment 1.Palm oil hydrogenation reaction evaluation result is in Table 1.
Embodiment 3
Change expanding agent in embodiment 1 into cetyl diethyl alcohol radical amine oxide 10.0g, other are with embodiment 1.Palm oil hydrogenation reaction evaluation result is in Table 1.
Embodiment 4
Change the addition of titanium tetrachloride in embodiment 1 into 330.0g, other are with embodiment 1.Palm oil hydrogenation reaction evaluation result is in Table 1.
Embodiment 5
Change auxiliary agent in embodiment 1 into magnesium chloride, magnesium chloride solution 150mL, concentration is 0.10mol/L, other are with embodiment 1.Palm oil hydrogenation reaction evaluation result is in Table 1.
Table 1. catalyst forms and palm oil hydrogenated products iodine number
Claims (1)
- The preparation method of 1.Yi Zhong large aperture oil hydrogenation catalyst, is characterized in that:The concrete operation step of Kaolinite Preparation of Catalyst is as follows:1) first certain density aluminum sulfate solution and sodium aluminate solution stream are joined in neutralization reaction still, it is 50-95 ℃ that whole reaction system keeps reaction temperature under mechanical agitation, within approximately 1 hour, neutralization reaction finishes, aging reaction liquid, control ageing time after 30-60 minute, appropriate titanium tetrachloride aqueous solution is squeezed in boehmite slurries, slowly added the ammoniacal liquor regulator solution pH to 6.5-7.5 of suitable concentration; Reaction finishes to continue aging 30-60 minute;2) aging end, keep temperature 60-90 ℃, nickel salts solution, the alkaline sedimentation agent solution, the compounding agent solution that have added amine oxide expanding agent are joined in neutralization reaction still, feed time was controlled in 1-2 hour, after neutralization reaction, keep synthermal aging 0.5-3.0 hour; Aging reaction solution finishes rear filtration slip, with deionized water, ethanol washing leaching cake post-drying, pulverizing, roasting, and at 300-500 ℃, logical N 2, H 2gaseous mixture: N 2/ H 2=3:1 volume ratio; Reduce 3-5 hour, add in stearic acid, stir, cooling curing granulating and forming gets final product to obtain oil hydrogenation catalyst;By above-mentioned preparation method, specific surface area of catalyst is 200-400m 2/ g, pore volume is 0.5-2.0m 3/ g, average pore size is 9-20nm; Catalyst consists of: effective active component nickel 5-30wt%, and auxiliary agent 0.01-5wt%, stearic acid 10-50wt%, all the other are titanium aluminum oxide carrier; With the total restatement of carrier, titanium oxide content is 0-50wt%;Described aluminum sulfate solution concentration is 0.10-2.00mol/L, and described sodium aluminate solution concentration is 2.00-6.00mol/L;The amine oxide expanding agent of described interpolation refers to one or both in the amino dimethyl oxidation of alkyl dimethyl amine oxide, alkyl diethyl alcohol radical Yang Huan and alkane acyl third amine, does not comprise other materials;The amine oxide expanding agent addition of described interpolation accounts for the 0.05-5% of catalyst quality;Described soluble nickel salting liquid is selected from as one or more in nickel chloride, nickelous sulfate, nickel nitrate or nickel acetate; Concentration is 5-30wt%;Described alkaline sedimentation agent solution is selected from one or more in sodium carbonate, sodium acid carbonate, sodium acetate, NaOH or ammonium bicarbonate soln; Concentration is 5-20wt%;Described compounding agent solution is one or more in nitrate, carbonate, acetate or the chloride solution of alkali earth metal; Concentration is 2-60wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368391A (en) * | 2014-11-10 | 2015-02-25 | 中国海洋石油总公司 | Hydrogenation catalyst with low trans-acid grease and preparation method thereof |
| CN106268824A (en) * | 2016-08-08 | 2017-01-04 | 农玉金 | A kind of C5 hydrogenation of petroleum resin Raney nickel and preparation method thereof |
| CN107541345A (en) * | 2017-10-31 | 2018-01-05 | 南通市康桥油脂有限公司 | A kind of recovery process of stearic acid hydrogenation catalyst |
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| US4510029A (en) * | 1984-05-18 | 1985-04-09 | Amax Inc. | Molten salt electrostripping cell and method for purifying molten salt electrolytes |
| CN101884929A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Fluid catalyst for preparing acrylonitrile by propylene ammoxidation |
| CN102029180A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Preparation method of catalyst for removing trace amounts of alkenes in reformate |
| CN102989462A (en) * | 2012-10-24 | 2013-03-27 | 中国海洋石油总公司 | Method for preparing oils and fats hydrogenation catalyst with high activity |
-
2013
- 2013-10-11 CN CN201310472730.7A patent/CN103506165B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4510029A (en) * | 1984-05-18 | 1985-04-09 | Amax Inc. | Molten salt electrostripping cell and method for purifying molten salt electrolytes |
| CN101884929A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Fluid catalyst for preparing acrylonitrile by propylene ammoxidation |
| CN102029180A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Preparation method of catalyst for removing trace amounts of alkenes in reformate |
| CN102989462A (en) * | 2012-10-24 | 2013-03-27 | 中国海洋石油总公司 | Method for preparing oils and fats hydrogenation catalyst with high activity |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368391A (en) * | 2014-11-10 | 2015-02-25 | 中国海洋石油总公司 | Hydrogenation catalyst with low trans-acid grease and preparation method thereof |
| CN104368391B (en) * | 2014-11-10 | 2016-09-14 | 中国海洋石油总公司 | A kind of low-antiform acid lipid hydrogenation catalyst and preparation method thereof |
| CN106268824A (en) * | 2016-08-08 | 2017-01-04 | 农玉金 | A kind of C5 hydrogenation of petroleum resin Raney nickel and preparation method thereof |
| CN106268824B (en) * | 2016-08-08 | 2019-01-01 | 广西驰胜农业科技有限公司 | A kind of C5 hydrogenation of petroleum resin Raney nickel and preparation method thereof |
| CN107541345A (en) * | 2017-10-31 | 2018-01-05 | 南通市康桥油脂有限公司 | A kind of recovery process of stearic acid hydrogenation catalyst |
| CN107541345B (en) * | 2017-10-31 | 2020-06-26 | 南通市康桥油脂有限公司 | Recovery process of stearic acid hydrogenation catalyst |
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| CN103506165B (en) | 2015-07-08 |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161008 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |